Reactive aldehyde chemistry explains the missing source of hydroxyl radicals
Abstract Hydroxyl radicals (OH) determine the tropospheric self-cleansing capacity, thus regulating air quality and climate. However, the state-of-the-art mechanisms still underestimate OH at low nitrogen oxide and high volatile organic compound regimes even considering the latest isoprene chemistry...
| Main Authors: | , , , , , , , , , , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2024-02-01
|
| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-45885-w |
| _version_ | 1797273958917079040 |
|---|---|
| author | Xinping Yang Haichao Wang Keding Lu Xuefei Ma Zhaofeng Tan Bo Long Xiaorui Chen Chunmeng Li Tianyu Zhai Yang Li Kun Qu Yu Xia Yuqiong Zhang Xin Li Shiyi Chen Huabin Dong Limin Zeng Yuanhang Zhang |
| author_facet | Xinping Yang Haichao Wang Keding Lu Xuefei Ma Zhaofeng Tan Bo Long Xiaorui Chen Chunmeng Li Tianyu Zhai Yang Li Kun Qu Yu Xia Yuqiong Zhang Xin Li Shiyi Chen Huabin Dong Limin Zeng Yuanhang Zhang |
| author_sort | Xinping Yang |
| collection | DOAJ |
| description | Abstract Hydroxyl radicals (OH) determine the tropospheric self-cleansing capacity, thus regulating air quality and climate. However, the state-of-the-art mechanisms still underestimate OH at low nitrogen oxide and high volatile organic compound regimes even considering the latest isoprene chemistry. Here we propose that the reactive aldehyde chemistry, especially the autoxidation of carbonyl organic peroxy radicals (R(CO)O2) derived from higher aldehydes, is a noteworthy OH regeneration mechanism that overwhelms the contribution of the isoprene autoxidation, the latter has been proved to largely contribute to the missing OH source under high isoprene condition. As diagnosed by the quantum chemical calculations, the R(CO)O2 radicals undergo fast H-migration to produce unsaturated hydroperoxyl-carbonyls that generate OH through rapid photolysis. This chemistry could explain almost all unknown OH sources in areas rich in both natural and anthropogenic emissions in the warm seasons, and may increasingly impact the global self-cleansing capacity in a future low nitrogen oxide society under carbon neutrality scenarios. |
| first_indexed | 2024-03-07T14:52:37Z |
| format | Article |
| id | doaj.art-761a377b4c824057b93fb4ecbd1bacd3 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-07T14:52:37Z |
| publishDate | 2024-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-761a377b4c824057b93fb4ecbd1bacd32024-03-05T19:38:31ZengNature PortfolioNature Communications2041-17232024-02-011511810.1038/s41467-024-45885-wReactive aldehyde chemistry explains the missing source of hydroxyl radicalsXinping Yang0Haichao Wang1Keding Lu2Xuefei Ma3Zhaofeng Tan4Bo Long5Xiaorui Chen6Chunmeng Li7Tianyu Zhai8Yang Li9Kun Qu10Yu Xia11Yuqiong Zhang12Xin Li13Shiyi Chen14Huabin Dong15Limin Zeng16Yuanhang Zhang17State Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversitySchool of Atmospheric Sciences, Sun Yat-sen University and Southern Marine Science and Engineering Guangdong Laboratory (Zhuhai)State Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityCollege of Material Science and Engineering, Guizhou Minzu UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityCollege of Material Science and Engineering, Guizhou Minzu UniversityCollege of Material Science and Engineering, Guizhou Minzu UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityState Key Joint Laboratory of Environmental Simulation and Pollution Control, State Environmental Protection Key Laboratory of Atmospheric Ozone Pollution Control, College of Environmental Sciences and Engineering, Peking UniversityAbstract Hydroxyl radicals (OH) determine the tropospheric self-cleansing capacity, thus regulating air quality and climate. However, the state-of-the-art mechanisms still underestimate OH at low nitrogen oxide and high volatile organic compound regimes even considering the latest isoprene chemistry. Here we propose that the reactive aldehyde chemistry, especially the autoxidation of carbonyl organic peroxy radicals (R(CO)O2) derived from higher aldehydes, is a noteworthy OH regeneration mechanism that overwhelms the contribution of the isoprene autoxidation, the latter has been proved to largely contribute to the missing OH source under high isoprene condition. As diagnosed by the quantum chemical calculations, the R(CO)O2 radicals undergo fast H-migration to produce unsaturated hydroperoxyl-carbonyls that generate OH through rapid photolysis. This chemistry could explain almost all unknown OH sources in areas rich in both natural and anthropogenic emissions in the warm seasons, and may increasingly impact the global self-cleansing capacity in a future low nitrogen oxide society under carbon neutrality scenarios.https://doi.org/10.1038/s41467-024-45885-w |
| spellingShingle | Xinping Yang Haichao Wang Keding Lu Xuefei Ma Zhaofeng Tan Bo Long Xiaorui Chen Chunmeng Li Tianyu Zhai Yang Li Kun Qu Yu Xia Yuqiong Zhang Xin Li Shiyi Chen Huabin Dong Limin Zeng Yuanhang Zhang Reactive aldehyde chemistry explains the missing source of hydroxyl radicals Nature Communications |
| title | Reactive aldehyde chemistry explains the missing source of hydroxyl radicals |
| title_full | Reactive aldehyde chemistry explains the missing source of hydroxyl radicals |
| title_fullStr | Reactive aldehyde chemistry explains the missing source of hydroxyl radicals |
| title_full_unstemmed | Reactive aldehyde chemistry explains the missing source of hydroxyl radicals |
| title_short | Reactive aldehyde chemistry explains the missing source of hydroxyl radicals |
| title_sort | reactive aldehyde chemistry explains the missing source of hydroxyl radicals |
| url | https://doi.org/10.1038/s41467-024-45885-w |
| work_keys_str_mv | AT xinpingyang reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT haichaowang reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT kedinglu reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT xuefeima reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT zhaofengtan reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT bolong reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT xiaoruichen reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT chunmengli reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT tianyuzhai reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT yangli reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT kunqu reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT yuxia reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT yuqiongzhang reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT xinli reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT shiyichen reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT huabindong reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT liminzeng reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals AT yuanhangzhang reactivealdehydechemistryexplainsthemissingsourceofhydroxylradicals |